Alkylphenol-alkylenepolyamine stabilizing composition



nited States ABSTRACT OF THE DISCLOSURE A stabilizing compositioncomprising a mixture of an alkylphenol and adialkylpolyhydroxyalkylalkylenepolyamine, exemplified by a mixture ofN,N-di-sec-octyl-N- hydroxyethylaminoethylethanolamine and from about 1%to about 75% by Weight thereof of 2,6-di-tertiarybutyl- 4-methylphenol.The composition is useful for stabilizing plastics and rubber, and as aninhibitor for gasoline and lube oil.

This is a continuation in part of copending application Ser. No.329,281, filed Dec. 9, 1963, and relates to a novel composition ofmatter comprising a mixture of chemical compounds of specificcomposition and configuration, as well as to the use thereof.

Parent application Ser. No. 329,281 describes a novel composition ofmatter of a specific chemical composition and configuration. Alsodisclosed in said parent application are mixtures of these chemicalcompounds with other chemical compounds. The mixture is a novelcomposition of matter and also possesses advantages for use as additivesto organic substrates.

The novel compounds claimed in the parent application are illustrated bythe following formula (Hi (LE 6-H where R is an alkyl group of from 4 toabout 50 carbon atoms, R is an alkylene group of from 2 to about 6carbon atoms, R" is an alkylene group of from 2 to about 6 carbon atomsand n is an integer of from to 4.

From the above formula, it will be seen that it is essential that eachnitrogen atom contains a hydroxyalkyl group attached thereto and thatthe terminal nitrogen atoms each contain an alkyl radical attachedthereto. This chemical configuration is essential in the compoundforming one component of the mixture of the present invention.

Referring to the formula hereinbefore set forth, when n is zero, thecompound is an N,N'-dialkyl-N-hydroxyalkylaminoalkyl-alkanolamine, whichalso may be named N,N'-dialkyl-N,N-dihydroxyalkyl-alkylenediamine. Thealkyl groups preferably are secondary alkyl groups and contain from 4 toabout 50 carbon atoms each and preferably from 4 to carbon atoms each.Illustrative preferred compounds in this embodiment includeN,N'-di-sec-butyl-N-hydroxyethyl-aminoethyl-ethanolamine,

N,N-di-sec-pentyl-N-hydroxyethyl-aminoethyl-ethanolamine,

N,N-di-sec-hexyl-N-hydroxyethyl-aminoethyl-ethanolamine,

N,N'-di-sec-heptyl-N-hydroxyethyl-aminoethyl-ethanolamine,

N,N-di-sec-octyl-N-hydroxyethyl-aminoethyl-ethanolamine,

atet

N,N'-di-sec-nonyl-N-hydroxyethyl-aminoethyl-ethanolamine,N,N'-di-sec-decyl-N-hydroxyethyl-aminoethyl-ethanolamine,N,N'-di-sec-undecyl-N-hydroxyethyl-aminoethyl-ethanolamine,N,N'-di-sec-dodecyl-N-hydroxyethyl-aminoethyl-ethanolamine,N,N-di-sec-tridecyl-N-hydroxyethyl-aminoethyl-ethanolamine,N,N-di-sec-pentadecyl-N-hydroxyethyl-arninoethylethanolamine,N,N-di-sec-hexadecyl-N-hydroxyethyl-aminoethylethanolamine,N,N-di-sec-heptadecyl-N-hydroxyethyl-aminoethylethanolamine,N,N-di-sec-octadecyl-N-hydroxyethyl-aminoethylethanolamine,N,N-di-sec-nonadecyl-N-hydroxyethyl-aminoethylethanolamine,N,N-di-sec-eicosyl-N-hydroxyethyl-aminoethyl-ethanolamine, etc.

The above compounds are illustrative of compounds in which R and R" eachcontain two carbon atoms. It is understood that corresponding compoundsare included in which one or both of the groups containing two carbonatoms are replaced by a group containing 3, 4, 5 or 6 carbon atoms.

Referring again to the above formula, when n is 1, the compound of thepresent invention is named N,N-bis- [N-alkyl-N (hydroxyalkyl)aminoalkylJ-alkanolamine which also can be named N ,N -dialkyl-N ,N ,N-tri-(hydroxyalkyl)-diall ylenetriamine. Here again, it will be notedthat each terminal nitrogen contains an alkyl group and each nitrogenatom contains a hydroxyalkyl group attached thereto. Illustrativepreferred compounds in this embodiment include N,N-bis- [N-sec-butyl-N-(Z-hydroxyethyl) -aminoethy1] ethanolamine,

N,N-bis- [N-se c-pentyl-N- Z-hydroxyethyl -am'inoethyl] ethanolamine,

N,N-bis- [N-sec-hexyl-N- (Z-hydroxyethyl) -aminoethyl] ethanolamine,

N,N-bis- [N-sec-heptyl-N- (2-hydroxyethyl)-aminoethy1] ethanolamine,

N,N-bis- N-sec-nonyl-N- 2 hydroxyethyl) -aminoethyl] ethanolamine,

N,N-bis- N-sec-decyl-N- (Z-hydroxyethyl) -aminoethyl] ethanolamine,

N,N-bis- [N-sec-undecyl-N- Z-hydroxyethyl -aminoethyl] -ethanolamine,

N, N-bis N-sec-dodecyl-N- Z-hydroxyethyl -aminoethyl] -ethanolamine,

N,N-bis- N-sec-tridecyl-N- Z-hydroxyethyl) -aminoethyl] -ethanolamine,

N,N-bis- N-sec-tetradecyl-N- Z-hydroxyethyl -aminoethyl] -ethanolamine,

N,N-bis- [N-sec-pentadecyl-N- 2-hydroxyethyl) -aminoe thyl]-ethanolamine,

N,N-bis- [N-sec-heXadecyl-N- Z-hydroxyethyl) -aminoethyl] -ethanolamine,

N,N-bis- N-sec-heptadecyl-N- (2-hydroxyethyl) -aminoethyl] ethanolamine,

N,N-bis- [N-sec-octadecyl-N- Z-hydroxyethyl) -aminoethyl] -ethanolamine,

N,N-bis- [N-sec-nonadecyl-N- 2-hydroxyethyl) -aminoethyl] -ethanolamine,

N,N-bis- [N-sec-eicosyl-N- 2-hydroxyethyl -aminoethyl] ethanolamine,etc. 1

3 Here again, one or both of the groups containing two carbon atoms maybe replaced by a group containing 3, 4, 5 or 6 carbon atoms.

When n is 2, the compound is an N ,N -dialkyl-N ,N N ,Ntetrahydroxyalkyl-alkylenepolyamine. Illustrative compounds in thisembodiment include N ,N -di-sec-butyl-N ,N ,N ,N -tetra-(2-hydroxyethyl) triethylenetetr amine, N ,N -di-sec-pentyl-N ,N ,N ,N-tetra- (Z-hydroxyethyl triethylenetetr amine, N ,N -di-sec-heXyl-N ,N,N ,N -tetra- (Z-hydroxyethyl) triethylenetetramine, N ,N-di-sec-heptyl-N ,N ,N ,N -tetra- (Z-hydroxyethyl) triethylenetetramine,N ,N -di-sec-octyl-N ,N ,N ,N -tetra- (Z-hydroxyethyl)triethylenetetramine, N ,N -di-sec-n0nyl-N ,N ,N ,N -tetra-(Z-hydroxyethyl) triethyleuetetramine, N ,N -di-sec-decyl-N ,N ,N ,N-tetra- (2-hydroxyethyl) triethylenetetramine, N ,N -di-sec-undecyl-N ,N,N ,N -tetra- (Z-hydroxyethyl) -triethylenetetramine, N ,N-di-sec-dodecyl-N ,N ,N ,N -tetra- (Z-hydroxyethyl)-triethylenetetramine, N ,N -di-sec-tridecyl-N ,N ,N ,N -tetra-(Z-hydroxyethyl) -triethylenetetramine, N ,N -di-sec-tetradecyl-N ,N ,N,N -tetra- (Z-hydroxyethyl -triethylenetetramine, N ,N-di-sec-pentadecyl-N ,N ,N ,N -tetra- (Z-hydroxyethyl)-triethylenetetramine, N ,N -di-sec-hexadecyl-N ,N ,N ,N -tetra-(2-hydroxyethyl) -triethylenetetramine, N ,N -di-sec-heptadecyl-N ,N ,N,N -tetra- (Z-hydroxyethyl) -triethylenetetramine, N ,N-di-sec-octadecy1-N ,N ,N ,N -tetra- (2-hydroxyethyl)-triethylenetetramine, N ,N -di-sec-nonadecyl-N ,N ,N ,N-tetra-(2-hydroxyethyl) -triethylenetetramine, N ,N -di-sec-eicosyl-N ,N,N ,N -tetra- (2-hydroxyethyl) -triethylenetetramine, etc.

Here again, it is understood that one or both of the groups containingtwo carbon atoms may be replaced by a group containing 3, 4, 5 or 6carbon atoms.

Referring again to the above formula, when n is 3, the compound will beN ,N -dialkyl-N ,N ,N ,N ,N -penta- (hydroxyalkyl)-alkylenepolyamine.Illustrative preferred compounds in this embodiment include N ,N-di-sec-butyl-N ,N ,N ,N ,N -penta- (Z-hydroxyethyl)-tetraethylenepentamine, N ,N -di-sec-pentyl-N ,N ,N ,N ,N -penta-(2-hydroxyethyl) -tetraethylenepentamine, N ,N -c1isec-hexyl-N ,N ,N ,N,N -penta- (2-hydroxyethyl) -tetraethylenepentamine, N ,N-di-sec-heptyl-1\l ,l I ,N ,N ,N -penta- (2-hydroxyethyl)-tetraethylenepentamine, N ,N -di-sec-octyl-N ,N ,N ,N ,N -penta-(2hydroxyethyl) -tetraethylenepentamine, N ,N -di-sec-nonyl-N ,N ,N ,N,N -penta- (2-hydroxyethyl) -tetraethylenepentamine, N ,N-di-sec-decyl-N ,N ,N ,N ,N -penta- (2-hydroxyethyl)-tetraethylenepentamine, N ,N -di-sec-undecyl-N ,N ,N ,N ,N -penta-(Z-hydroxyethyl) -tetraethylenep entamine, N ,N -di-sec-dodecyl-N ,N ,N,N ,N -penta- (Z-hydroxyethyl) -tetraethylenepent amine, N ,N-di-sec-tridecyl-N ,N ,N ,N ,N -penta- (Z-hydroxyethyl)-tetraethylenepentamine, N ,N -di-sec-tetradecyl-N ,N ,N ,N ,N -penta-(2-hydroxyethyl) -tetraethylenepentamine, N ,N -di-sec-pentadecyl-N ,N,N ,N ,N -penta- (2-hydroxyethyl) -tetraethylenepentamine, N ,N-di-sec-hexadecyl-N ,N ,N ,N ,N -penta- 2-hydroxyethyl)-tetraethylenepentamine,

N ,N -di-sec-heptadecyl-N ,N ,N ,N ,N -penta- (Z-hydroxyethyl)-tetraethylenepentamine, N ,N -di-sec-octadecyl-N ,N ,N ,N ,N -penta-(2-hydroxyethyl -tetraethylenepentamine, N ,N -di-sec-nonadecyl-N ,N ,N,N ,N -penta- Z-hydroxyethyl) -tetraethylenepentamine, N ,N-di-sec-eicosyl-N ,N ,N ,N ,N -penta-(Z-hydroxyethyl)-tetraethylenepentamine, etc.

Here again, it is understood that one or both of the groups containingtwo carbon atoms may be replaced by a group containing 3, 4, 5 or 6carbon atoms.

Referring again to the above formula, when n is 4, the compound will beN ,N -dialkyl-N ,N ,N ,N ,N ,N -hexa-(hydroxyalkyl)-pentaethylenehexamine. Illustrative preferred compoundsin this embodiment include N ,N -di-sec-butyl-N ,N ,N ,N ,N ,N -hexa-(Z-hydroxyethyl) -pentaethylenehexamine, N ,N -di-sec-pentyl-N ,N ,N ,N,N ,N -hexa- (Z-hydroxyethyl) -pentaethylenehex amine, N ,N-di-sec-hexyl-N ,N ,N ,N ,N ,N -hexa- (Z-hydroxyethyl)-pentaethylenehexamine, N ,N -di-sec-hepty1-N ,N ,N ,N ,N ,N heXa-(Z-hydroxyethyl) -pentaethylenehexamine, N ,N -di-sec-octyl-N ,N ,N ,N,N ,N -hexa- (Z-hydroxyethyl) -pentaethylenehexamine, N ,N-di-sec-nonyl-N ,N ,N ,N ,N ,N -hexa- (Z-hydroxyethyl)-pentaethylenehexamine, N ,N -di-sec-decyl-N ,N ,N ,N ,N ,N -hexa-(Z-hydroxyethyl) -pentaethylenehexamine, N ,N -di-sec-undecyl-N ,N ,N ,N,N ,N -hexa- (2-hydroxyethyl) -pentaethylenehexamine, N ,N-di-sec-dodecyl-N ,N ,N ,N ,N ,N -hexa- (2-hydroxyethyl)-pentaethylenehexamine, N ,N -di-sec-tridecyl-N ,N ,N ,N ,N ,N-hexa-(2-hydroxyethyl -pentaethylenehexamine, N ,N -di-sec-tetradecyl-N,N ,N ,N ,N ,N -hexa- (2-hydroxyethyl) -pentaethylenehexamine, N ,N-di-sec-pentadecyl-N ,N ,N ,N ,N ,N -heXa- (2- hy droxyethyl)-pentaethylenehexamine, N ,N -di-sec-hexadecyl-N ,N ,N ,N ,N ,N -hexa-(2- hydroxyethyl) -pentaethylenehexamin e, N ,N -di-sec-heptadecyl-N ,N,N ,N ,N ,N -hexa- (Z-hydroxyethyl) -pentaethylenehexamine, N ,N-di-sec-0ctadecyl-N ,N ,N ,N ,N ,N -hexa- (2-hydroxyethyl)-pentaethylenehex amine, N ,N -di-sec-nonadecyl-N ,N ,N ,N ,N ,N -hexa-2-hydroxyethyl) -pentaethylenehexamine, N ,N-di-sec-eicosyl-N ,N ,N ,N,N ,N -hexa- (2-hy droxyethyl -p entaethylenehexamine, etc.

Here again, it is understood that one or both of the groups containingtwo carbon atoms may be replaced by a group containing 3, 4, 5 or 6carbon atoms.

As hereinbefore set forth, in a preferred embodiment the alkyl groupsattached to the terminal nitrogen atoms are secondary alkyl groups. Inanother embodiment, these groups may be cycloalkyl groups andparticularly cyclohexyl, alkylcyclohexyl, dialkylcyclohexyl, etc.,although they may comprise cyclobutyl, cyclopentyl, cycloheptyl,cyclooctyl, etc., and alkylated derivatives thereof. The cycloalkylgroups may be considered as corresponding to secondary alkyl groups. Thesecondary alkyl configuration is definitely preferred although, whendesired, .the alkyl groups attached to the terminal nitrogen atoms maybe normal alkyl groups but not necessarily with equivalent results. 7

The compounds illustrated in the above formula are prepared by firstreductively alkylating an alkylenepolyamine and then subjecting theresultant alkylenepolyamine containing alkyl groups attached to theterminal nitrogen atoms to oxyalkylenation. Accordingly, theoxyalkylenation is performed on alkylenepolyamines containing onlysecondary nitrogen atoms. There are no primary nitrogen atoms availableand, therefore, will not result in the formation of a nitrogen atomcontaining two another advantage of the may be used without the matingspecific compounds in pure state. One such mixhydroxyalkyl groups. Ashereinbefore set forth, it is an essential requirement that thesecompounds comprise those in which the terminal nitrogen atoms eachcontain an alkyl group attached thereto and each of the nitrogen atomscontains one and only one hydroxyalkyl group attached thereto.

As hereinbefore set forth, the above compounds are prepared by firstsubjecting an alkylene polyamine to reductive alkylation. Thealkylenepolyamines include ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine andcorresponding alkylenepolyamines in which the ethylene group or groupsare replaced by propylene, butylene, pentylene and/or hexylene groups.In order to prepare the preferred compounds in which the alkyl groupsare of secondary alkyl groups, the reductive al kylation is effectedusing a ketone. Any suitable ketone may be used and will be selected toproduce the desired secondary alkyl groups to be attached to theterminal nitrogen atoms. Illustrative preferred ketones include methylethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl pentylketone, methyl hexyl ketone, methyl heptyl ketone, methyl octyl ketone,methyl nonyl ketone, methyl decyl ketone, methyl undecyl ketone, methyldodecyl ketone, methyl tridecyl ketone, methyl tetradecyl ketone, methylpentadecyl ketone, methyl hexadecyl ketone, methyl heptadecyl ketone,methyl octadecyl ketone, etc., diethyl ketone, ethyl propyl ketone,ethyl butyl ketone, ethyl pentyl ketone, ethyl hexyl ketone, ethylheptyl ketone, ethyl octyl ketone, ethyl nonyl ketone, ethyl decylketone, ethyl undecyl ketone, ethyl dodecyl ketone, ethyl tridecylketone, ethyl tetradecyl ketone, ethyl pentadecyl ketone, ethylhexadecyl ketone, ethyl heptadecyl ketone, etc., dipropyl ketone, propylbutyl ketone, propyl pentyl ketone, propyl hexyl ketone, propyl heptylketone, propyl octyl ketone, propyl nonyl ketone, propyl decyl ketone,propyl undecyl ketone, propyl dodecyl ketone, propyl tridecyl ketone,propyl tetradecyl ketone, propyl pentadecyl ketone, propyl hexadecylketone, etc., dibutyl ketone, butyl pentyl ketone, butyl hexyl ketone,butyl heptyl ketone, butyl octyl ketone, butyl nonyl ketone, butyl decylketone, butyl undecyl ketone, butyl dodecyl ketone, butyl tridecylketone, butyl tetradecyl ketone, butyl pentadecyl ketone, etc., dipentylketone, pentyl hexyl ketone, pentyl heptyl ketone, pentyl octyl ketone,pentyl nonyl ketone, pentyl decyl ketone, pentyl undecyl ketone, pentyldodecyl ketone, pentyl tridecyl ketone, pentyl tetradecyl ketone, etc.,dihexyl ketone, hexyl heptyl ketone, hexyl octyl ketone, hexyl nonylketone, hexyl decyl ketone, hexyl undecyl ketone, hexyl dodecyl ketone,hexyl tridecyl ketone etc., diheptyl ketone, heptyl octyl ketone, heptylnonyl ketone, heptyl decyl ketone, heptyl undecyl ketone, heptyl dodecylketone, etc., dioctyl ketone, octyl nonyl ketone, octyl decyl ketone,octyl undecyl ketone, etc., dinonyl ketone, nonyl decyl ketone, didecylketone, etc. It is understood that the ketones may be of straight orbranched chain configuration. Ketones are available commercially or theymay be synthesized as required. A number of ketones and particularly thehigher boiling ketones are available as mixtures which are eitherproducts or byproducts of commercial operations. These mixturesgenerally are available at comparatively low cost and, as presentinvention, the mixtures added time and expense of septure availablecommercially is Stearone which is diheptadecyl ketone.

The reductive alkylation of the ketone and alkylenepolyamine is effectedin any suitable manner. The reaction is effected using at least twomoles of ketone per mole of alkylenepolyamine and generally an excess ofthe ketone, which may range up to about twenty mole proportions ofketone per one mole proportion of alkylenepolyamine, is employed toinsure complete reaction. In one embodiment the reaction is effected inthe presence of hydrogen and a suitable alkylation catalyst in one step,which may be either continuous or batch type operation. Any suitablereductive alkylation catalyst is employed including those containingnickel, platinum palladium, etc., preferably composited with a suitablesupport. A particularly preferred catalyst comprises a composite ofplatinum and alumina, which may or may not contain combined halogen. Theplatinum generally is present in the catalyst in a concentration of fromabout 0.1 to about 2% by weight of the final catalyst and the halogen,when present, is in a concentration of total halogen of from about 0.01%to about 1% by Weight of the final catalyst, the halogen preferablycomprising fluorine and/or chlorine. Another suitable catalyst comprisesan intimate mixture of copper oxide, chromium oxide and barium oxide.When using the platinum catalyst, the temperature generally will bewithin the range of from about 200 to about 500 F. and a hydrogenpressure of from about to about 3000 pounds per square inch or more.

In a continuous type operation, the catalyst is disposed as a fixed bedin a reaction zone and the alkylenepolyamine, ketone and hydrogen, atthe required temperature and pressure, are passed through the catalystin either upward or downward flow. The reactor effluent is separatedinto a hydrogen stream and unreacted products, all or part of which maybe recycled to the reaction zone, and the desired terminally alkylatedalkylenepolyamine is separated from other high boiling products, if any.In a batch type operation, the alkylenepolyamine, ketone and catalystare disposed in a reaction zone which is pressured with hydrogen andthen heated to the desired temperature. After cooling, the products areseparated to recover the desired terminally alkylated alkylenepolyamine. While the one-step process generally is preferred, it isunderstood that the reaction may be effected in two steps. In the firststep, effected in the absence of hydrogen, the Schitfs base is firstprepared and then is hydrogenated in a separate step to form the desiredterminally alkylated alkylenepolyamine.

The terminally alkylated alkylenepolyamine, prepared in the abovemanner, then is subjected to oxyalkylenation.

The oxyalkylenation is readily effected by charging the terminallyalkylated alkylenepolyamine into a reaction zone and passing alkyleneoxide, particularly ethylene oxide, into contact with thealkylenepolyamine. The alkylene oxide will be used in a proportion of atleast one mole thereof per each nitrogen atom in the alkylenepolyamine.For example, when N,N'-dialkyl-ethylenediamine is to be oxyalkylenated,at least two moles of alkylene oxide are used per mole ofethylenediamine. Usually an excess of the alkylene oxide is employed inorder to insure complete reaction. This reaction readily occurs at a lowtemperature which may range from room temperature to 300 F. in theabsence of a catalyst. As hereinbefore set forth, ethylene oxide ispreferred. Other alkylene oxides include propylene oxide, butyleneoxide, pentylene oxide, hexylene oxide, etc., as well as styrene oxide,epichlorohydrin, etc. It is understood that the R alkylene group may besubstituted by such groups as phenyl, alkoxy, thio-oxy, halo, hydroxy,etc. It will be noted that the alkylated alkylenepolyamine contains onlysecondary nitrogen atoms and accordingly the oxyalkylenation will resultin each nitrogen atom containing only one oxyalkylene group.

In accordance with the present invention, the compound of the formulahereinbefore set forth is used in conjunction with another compound orcompounds and particularly an alkylphenol and more particularly atrialkylphenol. A specially preferred trialkylphenol is 2,6-ditertiary-butyl-4-methyl-phenol. Another preferred trialkylphenol is1,1,3 tris-(2-methyl-4-hydroxy-t-tertiarybutylphenyl)-butane. Othertrialkylphenols include 2,4- dimethyl-6-tertiarybutyl-phenol, 2446(American Cyanamid) [2,2' methylene-bis-(4-methyl-6-tertiary-butyl-phe-7 nol)], 425 (American Cyanamid) [2,2-methylene-bis-(4-ethyl-S-tertiarybutyl-phenol)], -702 (Ethyl Corporation) [4,4'methylene-bis-(2,6-ditertiarybutyl-phenol)], etc. Still otheralkylphenols include Santonox R, Santo- -white[4,4'-thiobis-(6-tertiarybutyl-meta-cresol)], Santothylamine, phenylbeta naphthylamine, phenothiazine,

Nonox WSP, Nonox C1, alkylalkoxyphenols, diphenylp-phenylenediamine,Salol (salicylic acid esters), poctyl-phenylsalicylate, various phosgenealkylated phenol reaction products, variousalkoxyalkyldihydroxybenzophenones, polyalkyldihydroxybenzophenones,tetrahydroxybenzophenones, 2,4,5 trihydroxybutyrophenone, various(hydroxy-alkylphenyl)-benzotriazoles,(hydroxyalkoxyphenol)-benzotriazoles, etc. Other compounds includenickel-bis-dithiocarbamates, nickel-bis dihydroxypolyalkylphenolsulfides, dilauryl beta-mercaptodipropionate, dihydroxytetraalkylsulfides, dihydroxytetraalkyl methanes, various trithiophosphites astrilaurylthiophosphite, dialkylphosphites, trialkylphosphites, highmolecular weight nitriles, various Mannich bases, etc.

As hereinbefore set forth, the mixture of the present invention offersadvantages for use as additive in organic substrates. For example,particularly improved results are obtained in the stabilization ofplastics, apparently due to a synergistic effect, when the compositionof the present invention contains a phenolic compound and particularly atrialkylphenol. The above compound will be used in the mixture in aconcentration of from about 1% to about 75% by weight of the compoundillustrated by the formula hereinbefore set forth. It is understood thatthe mixture of the present invention may be used in conjunction withother additives which are incorporated in the organic substrate forparticular purposes. Thus, the mixture of the present invention may beused in admixture with additional antioxidant, metal deactivator, dye,detergent, etc.

The novel mixtures of the present invention possess varied utility. Theyare of exceptional utility in substrates exposed to weather and in thisembodiment the mixtures of the present invention serve as weatheringstabilizers. Although the mechanism in which these mixtures function isnot completely understood, these mixtures serve to protect substrateswhich undergo ultraviolet light induced oxidation. It is believed thatthe mixtures of the present invention preferentially become oxidizedduring such ultraviolet exposure and form oxidized derivatives. Theoxidized derivatives apparently serve as effective weatheringstabilizers and thus the mixtures of the present invention appear uniquein effectively stabilizing the substrate for a long period of time. Inaddition, the mixtures of the present invention possess anti-staticproperties and adhesion improving properties. Furthermore, they are ofready solubility in most substrates. The substrates normally subject toexposure to weather include plastics, resins, paints, other coatings,etc. In addition the mixtures are useful as dye sites and by themselvesdo not impart color to the plastics, resins, paints or other coatings.

Illustrative plastics which are stabilized by the novel compounds of thepresent invention include polyolefins and particularly polyethylene,polypropylene, polybutylene, mixed ethylene propylene polymers, mixedethylene butylene polymers, mixed propylene butylene polymers, etc. Thesolid olefin polymers are used in many applications including electricalinsulation, lightweight outdoor furniture, awnings, cover forgreenhouses, etc. In many of these applications the solid olefin polymeris exposed to sunlight and air.

Another plastic being used commerically on a large scale is polystyrene.The polystyrene type resins are particularly useful in the manufactureof molded or machine articles which find application in such goods aswindows, optical goods, automobile panels, molded household articles,etc. One disadvantage of polystyrene is its tendency to deteriorate whenexposed to direct sunlight and air for extended periods of time.

Another class of plastics available cornmeri-cally is broadly classed asvinyl resins and is derived from monomers such as vinyl chloride, vinylacetate, vinylidine chloride, etc. Polyvinyl chloride plastics areavailable commercially on a large scale and undergo deterioration whenexposed to sunlight. Other vinyl type resins include copolymers of vinylchloride with acrylonitrile, methacrylonitrile, vinylidine chloride,alkyl acrylates, alkyl methacrylates, alkyl maleates, alkyl fumarates,polyvinyl butyral etc., or mixtures thereof.

Other plastics being used commercially on a large scale are in thetextile class and include nylon (polyamide), Perlon L or 6-nylon(polyamide), Dacron (terepthalic acid and ethylene glycol), Orlon(polyacrylonitrile), Dynel (copolymer of acrylonitrile and vinylchloride), Acrilan (polyacrylonitrile modified with vinyl acetate),Saran (copolymer of vinylidine chloride and vinyl chloride), rayon, etc.Here again, deterioration occurs due to ultraviolet light and oxidation.

Still other plastics are prepared from other monomers and are availablecommerically. Illustrative examples of such other solid polymers includephenolformaldehyde resins", urea-formaldehyde resins,melamine-formaldehyde resins, acryloid plastics which are derived frommethyl, ethyl and higher alkyl acrylates and methacrylates as monomersused in the polymerization. Also included in the solid polymers are thepolyurethane foams which are becoming increasingly available on a largescale and polyacetals, especially polyformaldehydes such as Delrin andCelcon. Still other resins are the epoxy resins which also are usedoutdoors and undergo deterioration due to ultraviolet light andoxidation. Other substrates include vinyl, urethane, acrylic,nitrocellulose based coatings; especially cellulose acetate, celluloseacetate butyrate, ethyl cellulose, etc. Still other substrates arepolyesters, including linear or cross-linked, reinforced polyesters,laminate polyesters, etc., various latexes, lacquers, alkyds, varnishes,polishes, stains, pigments, dyes, textile finishing formulations, etc.

It is understood that the plastic may be fabricated into any desiredfinished product including moldings, castings, fibers, films, sheets,rods, tubing or other shapes.

Rubber is composed of polymers of conjugated 1,3- dienes, either aspolymers thereof or as copolymers thereof with other polymerizablecompounds, and the rubbers, both natural and synthetic, are included assolid polymers in the present specifications and claims. Syntheticrubbers include SBR rubber (copolymer of butadiene and styrene), Buna N(copolymer of butadiene and acrylonitrile), butyl rubber (copolymer ofbutadiene and isobutylene), Neoprene rubber (chloroprene polymer),Thiokol .rubber (polysulfide), silicone rubber, etc. The natural rubbersinclude hevea rubber, cautchouc, balata, gutta percha, etc. It is wellknown that rubber undergoes deterioration due to oxygen and, whenexposed to direct sunlight for extended periods of time, also undergoesdeterioration from this source.

The above are illustrative examples of various plastics and resins whichare improved by the additives of the present invention. As hereinbeforeset forth, still other substrates include paints, varnishes, dryingoils, pigments,

rust preventive coatings, wax coatings, protective coatings, etc. It isunderstood that the compounds of the present invention may be used inany coating which is subject to exposure to ultraviolet light,oxidation, heat, etc. While the compounds are especially useful inmaterials subject to such exposure, it is understood that the compoundsof the present invention also may be used advantageously in othercoatings, plastics, resins, paints, etc., which normally are not exposedoutdoors.

The compounds of the present invention also are of utility as additivesin other organic substrates including, for example, hydrocarbondistillates. Illustrative hydrocarbon distillates include gasoline,naphtha, kerosene, jet fuel, solvents, fuel oil, burner oil, range oil,diesel oil, marine oil, turbine oil, cutting oil, rolling oil, solubleoil, drawing oil, slushing oil, lubricating oil, fingerprint remover,wax, fat, grease, etc. In the oils, the compounds of the presentinvention serve to inhibit oxidative deterioration, thermaldeterioration, etc., thereby retarding and/or preventing sedimentformation, dispersion of sediment when formed, preventing and/orretarding discoloration, rust or corrosion inhibitor, detergent, etc.

The additive mixture of the present invention will be used in astabilizing concentration which will depend upon the particularsubstrate. The additive mixture may be used in a concentration as low as0.001% to about 25% but generally will be used in a concentration offrom about 0.01% to about by weight of the substrate. The additivemixture is incorporated in the substrate in any suitable manner. Forexample, when it is incorporated into a plastic, resin or the like, itmay be added to the hot melt, generally in a Banbury mixer, extruder orother device. When it is added to a liquid, it is incorporated into theliquid with intimate stirring. When it is added to a multi-componentmixture as, for example, grease, it may be added to one of thecomponents and, in this manner, incorporated into the final mix or itmay be added directly into the final mix.

The additive mixture of the present invention may be utilized as such orprepared as a solution in a suitable solvent including alcohols andparticularly methanol, ethanol, propanol, butanol, etc., hydrocarbonsand particularly benzene, toluene, xylene, curnene, Decalin, etc.

The following examples are introduced to illustrate further the noveltyandutility of the present invention but not with the invention of undulylimiting the same.

Example I A compound for use in the mixture of the present invention isN,N di sec octyl-N-hydroxyethyl-aminoethylethanolamine [also can benamed N,N'-di-sec-octyl- N,N-di-(Z-hydroxyethyl)-ethylenediamine] andwas prepared by reacting one mole proportion of N,N'-bis-(1-methylheptyl)-ethylenediamine with two mole proportions of ethyleneoxide. The oxyethylenation was effected by intimately mixing thereactants in a turbomixer at a temperature of about 240 F. and apressure of about 250 psi. for about two hours. The product wasrecovered as a liquid boiling at 188 C. at 0.4 mm. Hg and having anindex of refraction n of 1.4705, basic nitrogen content of 5.37 meq./g.,hydroxyl content of 4.5 meq./ g. and a G.L.C. purity of 98%.

Example II Another compound for use in the mixture of the presentinvention is N,N bis [N-sec-octyl-N-(Z-hydroxyethyl)aminoethyl]-ethanolarnine, which also may be named N N di sec-octyl-N ,N,N -tri-(Z-hydroxyethyl)-diethylenetriamine. The compound was preparedby reacting one mole proportion of N ,N -bis-(1-ethyl-3-methylpentyl)-diethylenetriamine with three mole proportions of ethylene oxide in aturbomixer at a temperature of about 212 F. for four hours. The productwas recovered as a light colored liquid boiling at 233-235 C. at 0.5 mm.Hg having a basic nitrogen content of 6.58 meq./g. and a hydroxylcontent by acetylation method of 5.75 meql/ g.

readily seen that an additive which is exceptional and of high utility.

10 Example III A homogeneous mixture was prepared by dissolving 7.5parts by weight of 2,6-ditertiarybutyl-4-methylphenol in 100 parts byweight of N,N'-di-sec-octyl-N-hydroxyethylaminoethylethanolamine. Thebutylated hydroxytoluene was readily soluble in theN,N'-di-sec-octyl-N-hydroxyethylaminoethylethanolamine and resulted in ahomogeneous solution.

Example IV As hereinbefore set forth, the mixture of the presentinvention is of exceptional utility as an additive in plastics. Theplastic of this example is polyethylene. The polyethylene was a specialbatch of commercial polyethylene and was obtained free of inhibitors inorder that it may be used as a proper control sample to evaluate theeffect of the inhibitor. The solid polyethylene is of the high densitytype and the inhibited product is marketed cornmercially under the tradename of Fortifiex by the Celanese Corporation of America. Thepolyethylene was milled in a two-roll heated mill of conventionalcommercial design and the inhibitor was incorporated in the sampleduring the milling. The samples were pressed into sheets of about 17 milthickness and out into plaques of about 1%" x 1 /2". The plaques wereexposed to weathering on an outdoor rack facing south and inclined at a45 angle at Des Plaines, Ill. The samples were analyzed periodically byinfrared analysis and the intensity of the carbonyl band at 1715 cm. wasdetermined and reported as carbonyl number. The higher intensity of thecarbonyl band indicates a higher carbonyl concentration (expressed ascarbonyl number) and accordingly increased deterioration.

Deterioration of the polyolefin exposed outdoors increases rapidlyduring the late spring, summer and early fall months. A sample of thepolyethylene without inhibitor, when exposed outdoors in about themiddle of May, underwent an increase in carbonyl number to above 720 bythe end of August. Another sample of the same polyethylene without theinhibitor, when placed outdoors in the beginning of January, increasedin carbonyl number from an initial of about 25 to about by the beginningof May and then shot up to over 500 by the middle of July.

The additive of this example is the mixture of N,N-di-sec-octyl-N-hydroxyethyl-arninoethylethanolamine and butylatedhydroxytoluene described in Example III. The mixture was incorporated inthe polyethylene described above in a concentration of 1.075% by weight.The sample was placed outdoors at the end of April and, when evaluatedin the manner described above, the carbonyl number increased from aninitial of 20 to only about 48 by the middle of August and to only 71after 352 days. Accordingly, in almost a year, the carbonyl numberincrease was very low. This sample has been exposed outdoors for a totalof 526 days and the carbonyl number has increased to only 114 after thislong period of exposure. After 847 days of outdoor exposure, thecarbonyl number has increased to only 147. No brittleness, crazing orcracking has been observed at this time of exposure.

Another very important property of the additive mixture of the presentinvention is that the polyethylene remained white in color during all ofthe exposure. It is both very elfectively protects the plastic withoutcausing discoloration thereof Example V A mixture of butylatedhydroxytoluene and the compound of Example II also was evaluated as anadditive in by weight of butylated hydroxytoluene were incorporated inanother sample of the polyethylene described in Example IV. Thepolyethylenewas evaluated by outdoor exposure in the same manner asheretofore described. The sample was placed out-doors at the end ofApril and the carbonyl number increased-from an initial of 32 to only 95by the middle of September and to only 112 after 352 days (almost ayear)of outdoor exposure. After 526 days'the carbonyl number was only 180.Here again, no darkening, brittleness, crazing or cracking has beennoticed.

Example VI Evaluations of the polyethylene described in Example IV alsowere made in a Weather-Ometer. The Weather- Ometer was operated withoutthe use of water sprays. The samples of polyethylene were prepared insubstantially the same manner as described in Example IV and the plaqueswere inserted into plastic holders, afi'lxed onto a rotating drum' andexposed to carbon arc rays at about 125 F. in the Weather-Ometer. Hereagain, the samples were examined periodically by infrared analysis todeter- Evaluations in the Weather-Ometer also were made using anothersample of the polyethylene described in Example IV andcontaining 1% byweight of N,N-bis- [N-sec-octyl N(Z-hydroxyethyl)-aminoethyl]-ethanolamine, prepared as described inExample II, and 0.075%

by weight of butylated hydroxytoluene.

When evaluated in the Weather-Ometer in the same manner as described inExample VI, the polyethylene increased from an initial carbonyl numberof 32 to only 254 after 1392 hours. The sample remained White throughoutthe complete evaluation. Here again, the effectiveness of the inhibitormixture of the present invention is demonstrated.

Example VIII The additive mixture of this example comprised 1% by weightof N,N'-di-sec-octyl-N-hydroxyethyl-amino- ,ethylethanolamine, preparedas described in Example I, and 0.1% by weight of1,1,3-tris-(Z-methyl-4-hydroxy-5- tertiarybutylphenyl)-butane. Theadditive mixture .was incorporated in polyethylene in substantially thesame manner as described in Example IV, after which the polyethylene wasexposed outdoors and evaluated in the same manner. However, in thisevaluation the polyethylene-was -a special batch of a dilferentpolyethylene and was obtained free. of inhibitor.

'The following table reports the carbonyl number increase of samplesexposed outdoors for 257 days.

TABLE I I Carbonyl number -Additive: after 257 days outdoors None 10000.1% by wt. of 1,1,3 tris-(2methyl-4-hydroxy-S-tertiarybutyl-phenyl)-butane 600 1% by wt. ofN,N'-di-sec-octyl-N-hydroxyethyl-aminoethyl-ethanolamine and 0.1

by wt. "of 1,1,"3-tris-(2-methyl-4-hydroxy-5-tertiary-butyl-phenyl')-butane 97 w1tmn 1a2 days. p

From the data in the above table, it will be seen that the additivemixture served to effectively inhibit deterioration of the polyethylene.

Example IX Evaluations were made in the same manner as described inExample VIII, but using other samples of the polyethylene described inExample IV.

A sample of the polyethylene containing only 0.1% of1,1,3-tris-(2-methyl-4-hydroxy 5 tertiarybutyl-phenyl)- butane reached acarbonyl number of 492 after 271 days of outdoor exposure, but anothersample containing 0.1% of the above compound and 1% by weight ofN,N-disec-octyl N hydroxyethyl aminoethyl ethanolamine reached acarbonyl number of only after 271 days of outdoor exposure.

Example X The additive mixture of this example comprises 1% by weight ofN,N bis [N-sec-pentatriacontyl-N-(Z-hydroxyethyl) aminoethyl]ethanolamine and 0.2% by Weight of 2,2methylene-bis-(4-methyl-6-tertiarybutylphenol). The first mentionedcompound also may be named N ,N di-sec-pentatriacontyl-N ,N ,N-tri-(2-hydroxyethyl)-diethylenetriamine. It was prepared by firstreductively alkylating one mole proportion of diethylenetriamine withtwo mole proportions of pentatriacontanone to prepare N ,N dipentatriacontyl-diethylenetriamine. 108 g. (0.1 mole) of N ,N-di-pentatriacontyldiethylenetriamine then were reacted with 25 g. (0.4mole) of ethylene oxide at 212 F. for seven and onehalf hours. N,N bis[N-pentatriacontyl-N-(Z-hydroxyethyl)-aminoethyl]-ethanolamine wasrecovered as a solid having an equivalent weight of 463 whichcorresponds to the theoretical equivalent weight of 405.

The above additive mixture is used in a concentration of 1.5% by weightin polystyrene by being added to styrene and then the mixture ispolymerized by heating at a temperature of about 250 F. for seven days.The resulting resin is molded at a temperature of about 320 F. intoplates. The efiect of the additive is determined by exposing outdoorsthree plates containing the additive and three plates of polystyreneprepared in the same manner but not containing the additive. The samplesof polystyrene containing the additive will undergo substantially nodeterioration and will be substantially unchanged in color for a longperiod of time.

Example XI and without additive, are pressed into sheets and then may beevaluated eitherin the Weather-Ometer or by outdoor exposure. Thesamples containing the additive mixture of the present invention willresist deterioration when evaluated in either of these methods for aconsiderably longer period of time than the samples without additive.

Example XII The additive mixture of Example III is used in aconcentration of 0.001% by weight as an additive in burner oil. Theburner oil is evaluated in a method referred to as the Erdco Test. Inthis method, heated oil is passed through a filter, and the timerequired to develop a differential pressure across the filter of 25in.Hg is determined. It is apparent that the longer the time, the moreeffective is the a dditive. However ,'.with a very effective additive,the time to'reacha dilferential pressure across the filter of 25 in. Hgis lengthened beyond reasonable limits that the test is stopped afterabout 300 minutes and the differential pressure at that time isreported. A control sample of the burner oil (not containing anadditive) developed a differential pressure across the filter of 25 in.Hg in about 125 minutes. In contrast, the sam'ple of burner oilcontaining the additive of this example will develop a differentialpressure across the filter of less than 1 in. Hg after 300 minutes.

I claim as my invention:

1. A mixture consisting essentially of an alkylphenol selected from thegroup consisting of dialkyland trialkylphenols and a compound of thefollowing formula where R is an alkyl group of from 4 to about 50 carbonatoms, R is an alkylene group of from 2 to about 6 carbon atoms, R" isan alkylene group of from 2 to about 6 carbon atoms and n is an integerof from O to 4,

said mixture containing from about 1% to about 75% by S. The mixture ofclaim 1 wherein said compound isN,N-dialkyl-N-hydroxyalkyl-aminoalkyl-alkanolarnine.

6. The mixture of claim 1 being a mixture of N,N-disec octylN-hydroxyethyl-aminoeth ylethanolamine and from about 1% to about 75% byweight thereof of 2,6- di-tertiarylbutyl-4-methy1phenol.

7. The mixture of claim 1 being a mixture of N,N-disec octylN-hydroxyethyl-aminoethylethanolamine and from about 1% to about 75% byweight thereof of 1,1,3-tris-(2-methyl-4-hydroxy-tertiarybutyl-phenol)-butane.

8. The mixture of claim 1 being a mixture of N,N'-di-sec-octyl-N-hydroxyethyl-aminoethylethanolamine and from about 1% toabout 75 by weight thereof of 2,2- methylene-bis-(4-methyl-6-tertiary-butyl-phen0l) References Cited UNITED STATESPATENTS 3,155,625 11/1964 Long et al. 252404 X FOREIGN PATENTS 585,75410/1959 Canada.

OTHER REFERENCES Rosenwald et 211.: Industrial and EngineeringChemistry, vol. 42 (No. 1), January 1950, pp. 162-165.

LEON D. ROSDOL, Primary Examiner. I. GLUCK, Assistant Examiner.

